Process for producing aluminum chloride



Aug. 5 1924. 1,503,648

F. w. HALL PROCESS FOR PRODUCING ALUMINUM CHLORIDE Fil'ed March 15 1920 2 sxieezs-sneei 1 u lanue doz @513 M GI Form *1 Aug. 5, 192 1,503,648

F. W. HALL PROCESS FOR PRODUCING ALUMINUM CHLORIDE Filed March 15, 1920' -2 Sheets-Sheet 3 Q Q I R "I: I I Pg I I" I 3 h" I WV| l j *5 I N I] omtoz @51 am Patented Aug. 5, 1924 u ITED STATES FRANK W. HALL, PORT ARTHUR, TEXAS, ASSIGNOR TO THE TEXAS COMPANY, OF NEW YORK, N. Y., A CORPORATION OF TEXAS.

PROCESS FOR PRODUCING ALUMINUM CHLORIDE.

Application filed March 15, 1920. Serial no. 365,861.

To all whom it may concern:

Be it known that I, FRANK W. HALL, a citizen of the United States, and a" resident of Port Arthur, county of Jefferson, and

State of Texas, have invented certain new and useful Improvements inProcesses for Producing Aluminum Chloride, of which the following is a specification, reference'being had to the accompanying drawings, forming a partthereof.

My invention relates to the reduction of aluminum chloride and particularly to the manufacture of anhydrous aluminum chloride in relatively large quantities.

One object of my inventlon is to manufacture aluminum chloride by means of the reaction obtaining betweena suitable aluminum compound, such as alumina, carbon and chlorin at 'high temperatures and to makev the process a continuous one by utilizingthc spent ash formed in the reaction to form a seal in the discharge mechanism from the 'reacting chamber from which the spent materials are continuously removed.

Another object of my invention is to provide a process for the aforesaid purpose that shall utilize readily obtainable ingre-;

dients, and that shall be particularly adapted for use in the :oil industry in producing anhydrous chloride, suitable for use as a caltalyst in the treating and decomposition of 01 s. y I

Figure l is a partially sectional elevation of a retort, together with a suitable furnace and condenser, arranged and ada ted for practicing the process of my invention with "the exception of the initial steps.

Figure 2 is an elevation'of a coking\oven in which certain of the materials are prepared in condition to be introduced into the retort of Figure 1.

Figure 3 is a transverse sectional elevation of the coking oven.

Figure 4 is an elevation in detail of the charging mechanism for the retort shown in Flgure 1.

Figure 5 is an elevation in detail discharging mechanism.

Before describing the process with which my present invention is concerned I will describe the a paratus and then point out the way in whic it is used for carrying out my process. Y Y

Referring to the drawings: I

10 is a vertical retort having a chamber 0 of the barrel 11 which is heated by the gases from the furnace -12. The hot gases formed in the combustion chamber. 13 of the furnace pass through a flue 14, encircle the retort and escape through a discharge flue 15. Chlorin gas is introduced. into the retort through a gas inlet pipe 16. v

The retort is provided with a suitable charging mechanism for admitting materials into the retort in a continuous or peri odic manner so that the retort may always contain the necessary reaction materials. As clearly. shown in Figure 4 a hopper 17 is provided and is preferably arranged to receive heat in orderthat the charge may be preheated before it is admitted into the re tort. In the mechanism shown the hopper is placed outside the direct current of the furnace gases but is so positioned that it will receive the heat of radiation from the furnace. The materials are admitted into the hopper 17 through the lid 18 and the admission of the charge to the retort is controlled by the bell valve 19 operated by the rod 20. The valve 19 is more or less cone shaped and contains at its base an extension or flange member 21 having a groove 22 which is ada ted to engage the bottom of the hopper 17 w 1811 the valve is drawn upward in a closed osition. The groove 22 is adapted to contain a powdered or pulverized material such that when the valve is closed a While it is advanta cons to preheat the charge in the hopper 1 it also desirable in order to maintain the valve 19 in proper working condition that this valve should not be subjected to excessive heat. In order to keep the valve in a comparatively cool condition a cooling system is referab'ly provided.' This may be done y constructing the valve operatin rod 20 in the form of a pipe containing within it a smaller pipe 23,

these pipes terminating withinthehollow valve member 19 and the ipe 23 being preferably extended within the cone to a near its base, as illustrated. One pipe is connected to a suitable source of water, not shown, and, the other pipe forms the water outlet thus providing for a circulation of water through the hollow cone. The pipes 20 and 23 may conveniently terminate in a flexible hose, not shown, in order that the pipe 20 may be movable so as to operate the:

valve19, the pipes being held in position when the valve is closed in any convenient manner. I Y

The retort has a cylindrical extension or outlet 24 which terminates within a rotary pan 25, as clearly shown in Figure 5. The

. which carries a, pinion 30 which meshes with a gear wheel 31 on the bottom of the The grate 28 operates to support the material in the retort while it is being subjected to the chlorination treatment allowing the ash or finer particles to drop into the pan 25, thus the ash or spent material is continuously working out of the retort and discharging into the rotatino pan where the accumulated ash forms a seaI which prevents the exitof the gases and vapors from the retort. The discharge of the ash into the pan is accelerated by means of the scraper 32 which is rigidly secured to the extension 24 and which serves to remove the ash from the mouth of the extension and conduct it into the path of the stationary plow or scraper 33 which is mounted on a bracket or arm 34. The plow 33 is arranged to scrape the ash only to a given depth so that while the excess ash may be pushed over' the rim of the pan the ash' required for the-maintenance of the seal will not be disturbed. In this way the rotation of the pan causes the ash to be continuously discharged from the retort while at the same time a gas-tight seal is maintained in the dipcharge apparatus by means of the spent as 1.

I The aluminum chloride vapors generated are conducted by a vapor line 35 to any suitable type of condenser for collecting the product. I prefer to utilize the type of condenser illustrated which embodies features particularly adapted for use in the practice of the herein disclosed continuous process and comprises a plurality of sections 36, 37, 38, 39 having the connections 40, 41. 42. Each of the condenser sections is provided with a scraper 43 in order that the aluminum chloride deposited on the walls of the condenser may be scraped down into the bottom of the sections. In order that the product may be withdrawn without interfering with the continuity of the process and without admitting air to the condenser a num- -a suitable carbon-containing substance.

ber of hoppers 44, 45, 46, and 47 are preferably provided to receive the aluminum chloride collected in the respective condenser sections. The gates or valves 48 control. the outlets from the condenser sections to the hoppers and the outlets of the latter I vwith charging doors 55.

According to my invention I mix a suitable aluminum ore, such as bauxite, (which has first been dried out, if necessary) witip mixture of bauxite and soft coal with a suitable binder, such as acid sludge or pitch, may be utilized in my process. However, I prefer in the operation ot the present process to prepare a coking mixture in accordance with the process described in my co-pending application #S362,19 8, filed March 1, 1920. I prefer to employ a single substance capable of furnishing the carbon necessary for the reaction and also capable of acting as a binder for the mixture. This substance may be. a liquid at normal temperatures or it may be a semi-solid substance which is rendered liquid by the application of heat. A suitable pitch composed of bottoms from asphalt base oils or other suitable residues made from petroleum or coaltars may be employed. One of the best materials that I have used for this purpose is acid sludge which. is a well known by-product of oil refineries. In any event, according to my invention I utilize either alone or in combination with other carbon-containing materials, a suitable form of carbon in a mixture with a suitable aluminum ore such as bauxite.

When preparing the cokin mixture, the aluminum ore is'preferably re need to apowdered condition and is then mixed with the pitch, acid slud e or other carbon-containing material which has been heated, if necessary, resulting in the formation of a liquid In any case when the aluminum ore and carbon-containing materials have been sufiiciently mixed the mixture is introduced iflto the oven 53 and sufficient heat is applied to coke the mass. The pitch, and especially the acid sludge, is an excellent material to use in the preparation of the coking mixture which is especially susceptible to the subsequent chlorination treatment. V

The retort 11 is charged with the coked mixture and h'eatisv applied by means of the furnace 13. When the coked mixture .is at the proper temperature chlorin gasis introducedthrough the gas inlet 16 and 1S diffused through the mass reacting therewith to produce aluminum chloride vapors. The aluminum chloride passes through the vapor line into the condenser sections 36, 37, 38 and 39 where it is condensed as a solid anhydrous aluminum chloride. It collects on the walls of the condenser and is scraped off by means of the scraper '43 and from time to time removed into the ho pers.

' There is a relatively fine ash ormed in the retort which sifts through the grate 28 and passes out of the retort through the outlet 24. In order to carry out my process to the best. advantage thecoked mixture which is introduced into the retort contains an: excess of aluminum ore, that is, a somewhat larger proportion ofaluminum compound than is theoretically required to carry 1 .on the reaction obtaining between aluminum pended claims.

compound, carbon and. chlorin. This excess aluminum coin ound such as alumina insures the productlon of a fine white ash and facilitates the formation of an ash seal in the retort discharge mechanism. The excess ash is continuously discharged over the rim of the rotating pan by means of the plow 33 while at the same time there is constantly a quantity of ash in the rotating pan to form a gas-tightseal.

The charge within the retort is replenished by a continuous introduction of coked material through any suitable continuous dischargin device or if desired the coked mixture a er being preheated in the hopper 17 is admitted to theretort from time to time as needed so as to maintain a constant supply of coked mixture in the reaction zone and thus make the process a com tinuous one.

My invention may, of course, be practiced by any suitable apparatus, that shown and described being merely for purposes of illustration and I intend that only such limitations be imposed as are indicated in the ap- What I claim is: v

1. The process of makin aluminum chloridethat consists in charging a coked mixture of an aluminum compound and a reducing agent into a heated retort and main.-

taininga sup ly of the coked mixture therein, chlorinating the mixture, continuously withdrawing the spent material, and withdrawing the 'aluniinumchloride vapors.

2. The process of mak ngalummum chloride: that, consists in continuously maintaining a coked mixturez'of, analuminum compound and carbonin aheatedretort, passlng chlorin gasthrough-theqmixturein the retort, continuously removing the ash from the retort, at the bottom," and drawing off the aluminum chloridevapors v produced. 1

3. The process of making aluminum chloride thaticonsistsin admitting a coked mixture of aluminum oxidand-carbon into a heated retort, passing chlorin gas through the mixture inthe retort, 'addingfresh portions of the coked mixture to constantly maintain a supply in the retort, continuously removing the ash from, the retort, and drawing off and condensing the ailnminum chloride vapcirs.v produced. Y

'4} The process of malring aluminum chloride that consists in ,coking-a mixturenof aluminum compound and a carbon containing substance, introducing the coked mixture into an atmosphere of chlorin at reaction temperatures, continuously maintaining a supply of the coked mixture in the reaction chamber, continuously Withdrawing the ash formed from thezone of reaction, causing the ash to form a seal in the discharge outlet of'the reaction chamber while continuously discharging the; excess ash therefrom, and collecting the aluminum chlorideproduced. Y

,5. The process of making aluminumchloride by means of the reaction obtaining between alumina, carbon and chlorin that consists in introducing into a retort a coked alumina-carbon mixture containing an excess of alumina, reacting chlorin with the mixture to=form aluminum chloride vapors and ash, continuously removing the ash from the zone of reaction while maintaining a supply of alumina-carbon coke therein, causing the ash to form a seal in the retort outlet, continuously removing the excess ash therefrom and collecting the aluminum chloride formed.

6. The process of making aluminum chloride that consists in constantly maintaining a quantity of alumina-carbon coke in an atmosphere of chlorin atreaction temperatures and continuously removing from the reaction chamber the ash and aluminum chloride formed.

7. The process of making aluminum chloride that consists in charging a heated retort with an alumina-carbon coke, continuously passing chlorin into the retort to form aluminum chloride vapors and ash,- collecting the ash at the bottom of the retort so as to form a gas-tight seal in the outlet thereof, removing the excess ash therefrom, and condensing the aluminum chloride.

8. The process of making aluminum chloride by means of the reaction obtaining between alumina, carbon and chlorin that consists in'constantly maintaining a quantity of alumina-carbon coke in an atmosphere of chlorin at reaction temperatures, maintaining .an excess of alumina in the reaction zone to form a fine ash, causing said ash to accumulate at the base of the retort so as to form a gas-tight seal in the outlet thereof, continuously removing the excess ash and condensing the aluminum chloride.

9. The process of making aluminum chloride by means of the chlorination of an aluminum ore and carbon that consists in introducing a coked mixture of aluminum compound and carbon containing an excess of the aluminum compound, chlorinating the mixture to form aluminum chloride vapors and ash and removing the ash through a self-sealing joint to exclude extraneous gas.

10. In the manufacture of aluminum chloride by means of the reaction obtaining between aluminous and carbonaceous material and chlorin, the step that consists in withdrawing solid products formed in the reaction through a seal 'formed of said solid products.

11. In the'manufacture of aluminum chloride by means of the reaction obtaining between aluminous and carbonaceous material and chlorin, the step that consists in withdrawing ash formed through aself-sealing joint that precludes the escape of interior gases.

12. In the manufacture of aluminum chloride by means of the reaction obtaining between aluminous material and chlorin in presence of a reducing agent, the step that consists in withdrawing spent solid material from the reaction chamber through an outlet passage arranged and adapted to prevent any substantial interchange of gases between the interior of the chamber and the atmosphere. s

13. In the manufacture of aluminum ch10 I ride by means of the reaction obtaining between aluminous and carbonaceous material and chlorin, the step that consists in withdrawing ash formed through a passage ar-, ranged and adapted to prevent the escape of interior gases.

14. The process of making aluminum chloride that comprises heating aluminous material in the presence of a reducing agent and chlorin and withdrawing ash formed from the reaction chamber while the reaction is underway.

'15. The process of manufacturing alu-'.

minum chloride that comprises charging aluminous and carbonaceous material into a retort, heating the retort, introducing chlorin thereinto, withdrawing ash formed from the bottom of the retort while the reaction is underway and adding fresh charges of aluminous and carbonaceous material to maintain a supply thereof in the retort.

In witness whereof, I have hereunto set my hand'this 18th day of February, 1920.

FRANK w. HALL. 

